US3477974A - Process for the preparation of ester resins - Google Patents

Process for the preparation of ester resins Download PDF

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Publication number
US3477974A
US3477974A US617514A US3477974DA US3477974A US 3477974 A US3477974 A US 3477974A US 617514 A US617514 A US 617514A US 3477974D A US3477974D A US 3477974DA US 3477974 A US3477974 A US 3477974A
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United States
Prior art keywords
water
reaction
esterification
acid
carbon atoms
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Expired - Lifetime
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US617514A
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English (en)
Inventor
Albert W De Ruyter Steveninck
Johannes Beevendorp
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Shell USA Inc
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Shell Oil Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus

Definitions

  • Epoxy resin esters are prepared by esterification of glycidyl polyethers of polyhydric phenols with monocarboxylic acids (fatty acids, branched acids) in the presence of a catalyst of the group consisting of organic phosphines, arsines, and stibines (e.g., triphenyl phosphine).
  • Ester resins prepared by esterification of condensation products of epichlorohydrin and polyhydric phenols with fatty acids are known products, which are used on a large scale as binders in paints and varnishes.
  • Ester resins of this type are soluble in hydrocarbons such as xylene, and after application of the coating composition to the surface to be protected provide a hard, flexible and strongly adhesive coating, which is insoluble in solvents owing to cross-linking of the ester resin under the influence of oxygen from the air, or to cross-linking with other resins.
  • the esterification is usually carried out by heating the glycidyl polyethers with fatty acids at 200-260 C. with removal of the water formed by the reaction.
  • ester resins having improved properties can be obtained by the addition of small amounts of certain substances.
  • ester resins soluble in xylene are prepared by esterification of glycidyl polyethers of polyhydric phenols with monocarboxylic acids of elevated temperatures with splitting off of water, characterized in that a compound is added to the mixture of glycidyl polyether and monocarboxylic acid, which compound has the general formula IU-A-R in which A is an element from group V-A of the Periodic Table having an atomic Weight of between and 150, and R R and R each represent a hydrocarbon group having 148 carbon atoms.
  • the resin ester resins obtained according to the invention are light in color and display very little haze; in addition the viscosity and the acid number are surprisingly low.
  • glycidyl polyether of a polyhydric phenol preference is given to a glycidyl polyether of 2,2-bis-(4-hydroxyphenyl) propane.
  • Glycidyl polyethers of this type may be represented by the general formula:
  • R is the divalent group and n is an integer of, for example, 0 to 12.
  • the terminal glycidyl groups can be partially hydrated to CH -CH-CH;
  • glycidyl polyethers having a molecular weight of 7004,000 and an esterification value of -220 Particular preference is given to glycidyl polyethers of 2,2-bis(4-hydroxyphenyl) propane having molecular weights of 800-2,000.
  • the molecular weights given are therefore always average values.
  • monocarboxylic acids use may be made of saturated or unsaturated acids having preferably more than 8 carbon atoms per molecule, and mixtures of monocarboxylic acids.
  • fatty acids from drying oils such as linseed oil, tung oil, soybean oil, fish oil, cottonseed oil, oiticica oil, perilla oil, sunflower seed oil, and also dehydrated fatty acids from castor oil, tall oil and tall oil fatty acids; moreover, fatty acids from non-drying oils, such as castor oil, coconut oil; lauric acid, 2-ethylhexoic acid, colophony, and saturated aliphatic monocarboxylic acids, in which the carboxyl groups are bound to tertiary and/or quaternary carbon atoms (in this specification for the sake of brevity also referred to as branched monocarboxylic acids).
  • saturated aliphatic monocarboxylic acids in which the carboxyl groups are bound to tertiary and/or quaternary carbon atoms use may very suitably be made of the monocarboxylic acids obtained by reaction of formic acid or of carbon monoxide and water, with olefins under the influence of liquid acid catalysts, such as sulfuric acid, phosphoric acid or complex compounds of phosphoric acid, boron trifluoride and water.
  • monocarboxylic acids branched in the alpha position can be obtained by the Reppe process. Preference is given to branched monocarboxylic acids containing more than 8 carbon atoms per molecule.
  • acids from monoolefins having 8 to 18 carbon atoms per molecule. It is preferred to start from mixtures of olefins obtained by cracking paratfinic hydrocarbons, for instance petroleum fractions. In these mixtures branched and unbranched acyclic, as well as cycloaliphatic olefis may be present. As a result of the action of formic acid or of carbon monoxide and water a mixture of saturated acylic and cycloaliphatic monocarboxylic acids is obtained from these mixtures.
  • A is, for example, phosphorus, arsenic or antimony.
  • the groups R R and R can be alkyl, cycloalkyl, alkyl cycloalkyl, aryl and alkaryl groups.
  • phosphines of the general formula PR in which R represents an aryl group or an alkyl group having l-18 carbon atoms such as triphenyl phosphine, tri-n-butyl phosphine trioctyl phosphine trilauryl phosphine trihexadecyl phosphine and trioctadecyl phosphine.
  • arsines and stibines are triphenylarsine tricyclohexylarsine, tributylstibine and triphenylstibine.
  • alkaline-reacting substances can also be added in small amounts, such as sodium carbonate, sodium bicarbonate, sodium hydroxide, calcium oxide, zinc oxide or salts soluble in organic solvents, for instance the naphthenates of the above metals.
  • the esterification is preferably carried out in an inert, oxygen-free atmosphere, for example, by passing nitrogen or carbon dioxide through or over the reaction mixture.
  • the esterification is preferably carried out at temperatures of from 200 C.-260 0.; higher or lower temperatures may also be used at some stages. For example, it is possible to keep the temperature at 150 C.200 C. to begin with, and to esterify further at temperatures above 200 C., preferably 230260 C. Such a choice of reaction temperatures is preferred when branched monocarboxylic acids are first added, followed by unbranched monocarboxylic acids such as ethylenically unsaturated fatty acids.
  • the esterification is an equilibrium reaction the water formed has to be removed in order to obtain as complete an esterification as possible.
  • the simplest method is to remove the water in the vapor state by passing a stream of inert gas through it.
  • a preferable method is to remove the water by azeotropic distillation with a small amount of xylene, for example 3% by weight, based on the total weight of reactants, the water being separated from the xylene, in a, water trap after cooling.
  • the ester resins prepared according to the invention are solid, semi-solid or highly viscous liquids at room temperature.
  • the viscosity in solution, which is of interest for the applications is usually determined in a 50% or 60% by weight solution in xylene at 25 C.
  • Ester resins prepared from ethylenically unsaturated fatty acids can be used in air-drying paint compositions, it being possible to accelerate the drying process by means of elevated temperatures and/or the addition of driers,
  • Ester resins. containing free hydroxyl groups can also be used in baking enamel composittions, together with urea-formaldehyde resins, melamine-formaldehyde resins and the like.
  • the invention is illustrated by some examples.
  • the Polyether E used in Examples I-XII was a condensation product of epichlorohydrin with 2,2-bis(4hydroxyphenyl) propane having the following properties:
  • Viscosity (40% byweight solution in butyl Dioxito1) By Gardner-Holdt method R-S Durran softening point, C. 99
  • the degree of haze is the percentage of diffused light.
  • the branched monocarboxylic acids used in Example XIII were obtained by reaction of olefins containing .8 to 10 carbon atoms per molecule with carbon monoxide and water in the presence of a catalyst, consisting of phosphoric acid, boron trifluoride and Water, these mono carboxylic acids containing 9 to 11 carbon atoms per molecule, and the carboxyl groups are bound to tertiary and/or quaternary carbon atoms.
  • EXAMPLE I In a one-liter reaction flask provided with stirrer, thermometer, gas inlet tube, reflux condenser with water trap, and heating jacket 164 g. of dehydrated castor oil fatty acids (40 parts by weight), 246 g. of Polyether E parts by weight), 40 ml. of xylene, and 0.4 milliequivalents of triphenyl phosphine per 100 g. of Polyether B were heated to 240 C. for 30 minutes with stirring, carbon dioxide being passed through, and maintained at this temperature for 4 hours while the water formed was continuously removed by azeotropic distillation with xylene. The flask with contents was subsequently cooled.
  • the ester resin had the properties shown in Table I.
  • the esters had the properties shown in Table 1; comparison with the esters prepared according to Examples I-VII shows that particularly the acid number and the degree of haze are considerably higher.
  • the viscosity is such as cobalt naphthenate, manganese naphthenate, lead 60 also noticeably higher, and the ester has a darker color.
  • the mixture was maintained at 170 C. for 60 minutes; the acid number was then 5.5. 1925 g. of linseed Degree of oil fatty acids were added and the temperature was ralsed to 240 C., and maintained at this level for 6 hours, with continuous removal of the water by azeotropic distillation with xylene.
  • the acid number of the ester resin obtained was 21.1.
  • R R and R have tthe same meanings as in claim 1, are added per 100 g. of glycidyl polyether.
  • a process as in claim 1 wherein the monocarboxylic acid is an alpha-branched, saturated, aliphatic monocarboxylic acid containing 9 to 11 carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paints Or Removers (AREA)
US617514A 1966-02-22 1967-02-21 Process for the preparation of ester resins Expired - Lifetime US3477974A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL6602241A NL6602241A (es) 1966-02-22 1966-02-22

Publications (1)

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US3477974A true US3477974A (en) 1969-11-11

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Country Status (7)

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US (1) US3477974A (es)
BE (1) BE694309A (es)
DE (1) DE1745369B2 (es)
FR (1) FR1512003A (es)
GB (1) GB1110208A (es)
NL (2) NL6602241A (es)
SE (1) SE337478B (es)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888808A (en) * 1972-09-29 1975-06-10 Mobil Oil Corp Tall oil epoxy ester exterior coating for lap-seam beverage cans
US3949895A (en) * 1973-11-30 1976-04-13 Mobil Oil Corporation Epoxy exterior coating for lap-seam beverage cans
EP0166314A2 (de) * 1984-06-16 1986-01-02 BASF Aktiengesellschaft Verfahren zur Herstellung Amidgruppen enthaltender Epoxid/Amin-Addukte
US4956109A (en) * 1988-05-30 1990-09-11 The Nisshin Oil Mills, Ltd. Lubricating oil
US5043387A (en) * 1988-04-04 1991-08-27 Mitsui Petrochemical Industries, Ltd. Epoxy resin reacted with primary amine, active hydrogen compound and esterifying agent to yield polyol resin
US5268435A (en) * 1988-04-04 1993-12-07 Mitsui Petrochemical Industries, Ltd. Epoxy resin reacted with primary amine active hydrogen compound and esterifying agent to yield polyol resin
US5777013A (en) * 1997-01-24 1998-07-07 Arizona Chemical Company Dispersion and adhesion of silica in elastomeric materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2575440A (en) * 1948-11-16 1951-11-20 Shell Dev Crotonate esters of glyceryl polyethers of dihydric phenols
US2768153A (en) * 1955-02-24 1956-10-23 Shell Dev Process for curing polyepoxides and resulting products
US2970983A (en) * 1956-09-10 1961-02-07 Shell Oil Co Epoxy-containing condensates of polyepoxides and acidic materials, their preparation and polymers
US3301743A (en) * 1963-06-12 1967-01-31 Robertson Co H H Polyhydroxy polyacrylate esters of epoxidized phenol-formaldehyde novolac resins and laminates therefrom
US3377406A (en) * 1963-12-16 1968-04-09 Shell Oil Co Process of esterification of polyepoxides with ethylenically unsaturated monocarboxylic acids in the presence of onium salts of inorganic acids

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2575440A (en) * 1948-11-16 1951-11-20 Shell Dev Crotonate esters of glyceryl polyethers of dihydric phenols
US2768153A (en) * 1955-02-24 1956-10-23 Shell Dev Process for curing polyepoxides and resulting products
US2970983A (en) * 1956-09-10 1961-02-07 Shell Oil Co Epoxy-containing condensates of polyepoxides and acidic materials, their preparation and polymers
US3301743A (en) * 1963-06-12 1967-01-31 Robertson Co H H Polyhydroxy polyacrylate esters of epoxidized phenol-formaldehyde novolac resins and laminates therefrom
US3377406A (en) * 1963-12-16 1968-04-09 Shell Oil Co Process of esterification of polyepoxides with ethylenically unsaturated monocarboxylic acids in the presence of onium salts of inorganic acids

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888808A (en) * 1972-09-29 1975-06-10 Mobil Oil Corp Tall oil epoxy ester exterior coating for lap-seam beverage cans
US3949895A (en) * 1973-11-30 1976-04-13 Mobil Oil Corporation Epoxy exterior coating for lap-seam beverage cans
EP0166314A2 (de) * 1984-06-16 1986-01-02 BASF Aktiengesellschaft Verfahren zur Herstellung Amidgruppen enthaltender Epoxid/Amin-Addukte
EP0166314A3 (en) * 1984-06-16 1986-12-30 Basf Aktiengesellschaft Process for the preparation of epoxy/amide adducts containing amide groups
US5043387A (en) * 1988-04-04 1991-08-27 Mitsui Petrochemical Industries, Ltd. Epoxy resin reacted with primary amine, active hydrogen compound and esterifying agent to yield polyol resin
US5268435A (en) * 1988-04-04 1993-12-07 Mitsui Petrochemical Industries, Ltd. Epoxy resin reacted with primary amine active hydrogen compound and esterifying agent to yield polyol resin
US4956109A (en) * 1988-05-30 1990-09-11 The Nisshin Oil Mills, Ltd. Lubricating oil
US5777013A (en) * 1997-01-24 1998-07-07 Arizona Chemical Company Dispersion and adhesion of silica in elastomeric materials

Also Published As

Publication number Publication date
GB1110208A (en) 1968-04-18
FR1512003A (fr) 1968-02-02
DE1745369B2 (de) 1976-11-04
NL128836C (es)
BE694309A (es) 1967-08-21
NL6602241A (es) 1967-08-23
SE337478B (es) 1971-08-09
DE1745369A1 (de) 1971-09-02

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